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United States Patent |
5,607,481
|
Russ
,   et al.
|
March 4, 1997
|
Fiber-reactive anthraquinone dyes
Abstract
Fiber-reactive anthraquinone dyes Anthraquinone dyes of the formula (1)
##STR1##
in which the variables are defined in the disclosure, exhibit excellent
fastness properties, in particular chlorine fastness, light fastness and
wash fastness, and give good fixation yields.
Inventors:
|
Russ; Werner H. (Florsheim, DE);
Schumacher; Christian (Kelkheim, DE)
|
Assignee:
|
Hoechst Aktiengesellschaft (DE)
|
Appl. No.:
|
600828 |
Filed:
|
February 13, 1996 |
Current U.S. Class: |
8/463; 8/549; 8/676; 8/677; 8/678; 8/679; 8/918; 8/924; 544/189 |
Intern'l Class: |
D06P 005/15; D06P 001/382; D06P 001/384; C07D 251/40 |
Field of Search: |
544/187-189
8/549,676,677,678,679,463
|
References Cited
U.S. Patent Documents
4436906 | Mar., 1984 | Niwa et al. | 544/187.
|
5393884 | Feb., 1995 | Pedemonte et al. | 544/189.
|
Foreign Patent Documents |
94/29282 | Dec., 1994 | WO.
| |
Primary Examiner: Einsmann; Margaret
Attorney, Agent or Firm: Connolly & Hutz
Claims
We claim:
1. An anthraquinone compound of the formula (1),
##STR23##
in which R.sup.1 is hydrogen, C.sub.1 -C.sub.6 -alkylcarbonyl, C.sub.6
-arylcarbonyl, C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl or
phenyl where C.sub.1 -C.sub.6 -alkyl, C.sub.6 arylcarbonyl C.sub.3
-C.sub.6 -cycloalkyl and phenyl can be substituted by one or more radicals
selected from the group consisting of hydroxyl, sulfo, carboxyl, C.sub.1
-C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen, cyano, amino and
nitro,
R.sup.2 is sulfo or carboxyl,
m is 0 to 2,
R.sup.3 is sulfo, carboxyl or halogen,
n is 0 or 1,
R.sup.4 is sulfo, carboxyl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4
-alkoxy,
p is 0 to 2,
W is a C.sub.1 -C.sub.6 -alkylene group,
Y is vinyl or --CH.sub.2 CH.sub.2 -L where L is a group which can be
eliminated under alkaline conditions,
M is hydrogen or an alkali metal or a stoichiometric equivalent of an
alkaline earth metal,
q is 0 or 1, and
X is halogen, hydroxyl, C.sub.1 -C.sub.4 -alkyloxy, C.sub.6 -aryloxy,
cyanamino, amino, carboxy-(C.sub.1 -C.sub.4)-alkylamino, C.sub.1 -C.sub.4
-alkylamino, di-(C.sub.1 -C.sub.4 -alkyl)amino or C.sub.6 -arylamino where
the alkyl and aryl radicals of the alkylamino and arylamino groups
mentioned are unsubstituted or contain 1 to 5 substituents selected from
the group consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl,
sulfo, sulfato, C.sub.1 -C.sub.4 -alkylsulfonyl, C.sub.6 -arylsulfonyl,
halogen, cyano and nitro; or is the radical of a heterocyclic or aliphatic
amine which may contain 1 or 2 further hetero atoms selected from the
group consisting of N, O and S and can be substituted by a carboxyl
radical or an aminocarbonyl radical; or is the group --NR.sup.9 R.sup.10
R.sup.11 in which R.sup.9, R.sup.10 and R.sup.11, independently of one
another, are hydrogen or C.sub.1 -C.sub.4 -alkyl.
2. An anthraquinone compound as claimed in claim 1, wherein
R.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.5 -C.sub.6 -cycloalkyl,
acetyl, benzoyl, phenyl or methylphenylcarbonyl or C.sub.1 -C.sub.4
-alkyl, C.sub.5 -C.sub.6 -cycloalkyl or phenyl each of which is
substituted by 1 to 3 radicals selected from the group consisting of
hydroxyl, sulfo, carboxyl, methyl, ethyl, methoxy, ethoxy, fluorine,
chlorine, bromine, cyano and nitro.
3. An anthraquinone compound as claimed in claim 1, wherein R.sup.3 is
chlorine, bromine or a sulfo group which is in the ortho position relative
to the NH-R.sup.1 group.
4. An anthraquinone compound as claimed in claim 1, wherein W is C.sub.2
-C.sub.3 -alkylene.
5. An anthraquinone compound as claimed in claim 1, wherein W is
1,2-ethylene or 1,3-propylene.
6. An anthraquinone compound as claimed in claim 1, wherein L is chlorine,
bromine, --OSO.sub.3 M, --SSO.sub.3 M or --OPO.sub.3 M.sub.2 where M is
hydrogen or an alkali metal.
7. An anthraquinone compound as claimed in claim 1, wherein
m is 0,
n is 1,
p is 0 or 1, and
q is 0.
8. An anthraquinonecompoundasclaimedinclaim 1, wherein
X is fluorine, chlorine, cyanamino, amine, carboxymethylamino,
.beta.-carboxyethylamino, .beta.-sulfoethylamino,
N-methyl-.beta.-sulfoethylamino, .beta.-sulfatoethylamino,
.beta.-hydroxyethylamino, bis(.beta.-hydroxyethyl)amino, pyrrolidino,
piperidino, piperazino, morpholino, pyridin-1-yl, 3-carboxypyridin-1-yl,
3-aminocarbonylpyridin-1-yl or trimethylammonium.
9. An anthraquinone compound as claimed in claim 1, wherein the
anthraquinone compound has the formula (1a), (1b), (1c), (1d), (1e) or
(1f)
##STR24##
in which x is 2 or 3,
X.sup.1 is chlorine or fluorine,
R.sup.5 is methyl, ethyl or phenyl,
A is amino, carboxymethylamino, .beta.-carboxyethylamino,
.beta.-sulfoethylamino, N-methyl-.beta.-sulfoethylamino,
.beta.-sulfatoethylamino, .beta.-hydroxyethylamino,
bis(.beta.-hydroxyethyl)amino, morpholino, piperidino, pyrrolidino or
trimethylammonium,
R.sup.8 is hydrogen, aminocarbonyl or carboxyl,
Y.sup.1 is .beta.-sulfatoethyl, .beta.-chloroethyl or vinyl and p.sup.1 is
O or one.
10. A process for preparing a compound as claimed in claim 1, which process
comprises reacting a compound of the formula (2)
##STR25##
in which A is fluorine, chlorine, bromine, iodine, sulfo or nitro, with a
compound of the formula (3)
##STR26##
in the presence of a copper(I) or a copper(II) compound or a mixture
thereof, to give a compound of the formula (4)
##STR27##
and reacting the compound of the formula (4) either with a compound of the
formula (5)
##STR28##
in which X.sup.2 is halogen, to give the compound of the formula (1), or
reacting the compound of the formula (4) first with a compound of the
formula (6)
##STR29##
to give a compound of the formula (7)
##STR30##
and reacting the compound of the formula (7) with an amine of the formula
(8)
##STR31##
to give the compound of the formula (1).
11. The process as claimed in claim 10, wherein the copper(II) compound is
copper(II) sulfate, copper(II) nitrate, copper(II) chloride, copper(II)
bromide, copper(II) carbonate or copper(II) hydroxide.
12. A process for preparing an anthraquinone compound (1) as in claim 1 of
the formula (1A)
##STR32##
in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, W, Y, M, m, n, p and q have
one of the meanings defined in claim 1 and X.sup.10 is amino, cyanamino,
carboxy-(C.sub.1 -C.sub.4)-alkylamino, C.sub.1 -C.sub.4 -alkylamino,
di-(C.sub.1 -C.sub.4 -alkyl) amino, C.sub.6 -arylamino where the alkyl and
aryl radicals of the alkylamino and arylamino groups mentioned are
unsubstituted or contain 1 to 5 substituents selected from the group
consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl, sulfo,
sulfato, C.sub.1 -C.sub.4 -alkylsulfonyl, C.sub.6 -arylsulfonyl, halogen,
cyano and nitro, or is the radical of a heterocyclic or aliphatic amine,
which may contain 1 to 2 further hetero atoms selected from the group
consisting of N, O and S and can be substituted by a carboxyl radical or
an aminocarbonyl radical, or is the group --NR.sup.9 R.sup.10 R.sup.11 in
which R.sup.9, R.sup.10 and R.sup.11, independently of one another, are
hydrogen or C.sub.1 -C.sub.4 -alkyl,
which process comprises reacting an anthraquinone compound of the formula
(1B)
##STR33##
in which X.sup.20 is chlorine or fluorine, with ammonia, H.sub.2 NCN, a
carboxy-(C.sub.1 -C.sub.4)-alkylamine, C.sub.1 -C.sub.4 -alkylamine,
di-(C.sub.1 -C.sub.4 -alkyl)aznine, C.sub.6 -arylamine where the alkyl and
aryl radicals of the alkylamino and arylamino groups mentioned are
unsubstituted or contain 1 to 5 substituents selected from the group
consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl, sulfo,
sulfato, C.sub.1 -C.sub.4 -alkylsulfonyl, C.sub.6 -arylsulfonyl, halogen,
cyano and nitro, or with a heterocyclic or aliphatic amine, which may
contain 1 to 2 further hetero atoms selected from the group consisting of
N, O and S and can be substituted by a carboxyl radical or an
aminocarbonyl radical, or with a mono-, di- or tri-(C.sub.1 -C.sub.4
-alkyl)ammonium salt.
13. A method for dyeing or printing a hydroxyl-, mercapto-, amino- or
carboxamido-containing material or a material containing a combination of
these groups comprising the step of dyeing or printing said material with
an anthraquinone compound of the formula (1) as claimed in claim 1.
14. The method as claimed in claim 13, wherein the dyeing is a textile
printing method or a short-liquor pad-dyeing method.
15. A method for discharge printing a hydroxyl-, mercapto-, amino- or
carboxamido-containing material or a material containing a combination of
these groups comprising the step of discharge printing said material with
an anthraquinone compound as claimed in claim 9.
Description
The present invention is in the technical field of anthraquinoid
fiber-reactive dyes.
Anthraquinone dyes have been widely described in the literature. They are
distinguished by their brilliance, good light fastness properties and the
stability of the chromophore, not only under acidic, but also under basic
conditions. However, they have the disadvantage of high raw material costs
and comparatively low molar extinction. For this reason, when dyeing and
printing substrates, it is important that the dyes not only have superior
fastness properties and improved process characteristics, but can also be
prepared at competitive costs.
Almost all important anthraquinoid reactive dyes are derivatives of
bromamine acid (4-bromo-1-aminoanthraquinone-2-sulfonic acid), which in
most cases is reacted with a fiber-reactive amine component, in which the
fiber-reactive group can be linked to the amino group through aliphatic
or, more frequently, aromatic bridging members (A. H. M. Renfrew, Rev.
Prog. Color. Relat. Top. 15 (1985) 15).
One of the most important known reactive dyes for preparing brilliant,
fast, blue reactive dyeings on textiles is C.I. Reactive Blue 19 of the
formula (A), which was mentioned for the first time in DE-A-965,902. The
course of the synthesis has been described in numerous publications.
##STR2##
In most cases, the known anthraquinone dyes have the disadvantage that
their synthesis is complicated, resulting in unsatisfactory product and
space-time yields. Other brilliant blue dyes, for example azo dyes, often
require metal complexation for achieving good fastness properties, a
procedure which increasingly gives rise to environmental concern.
PCT/US 94/06727 describes anthraquinone dyes containing a fiber-reactive
triazine radical linked through a p-aminophenol unit. However, these dyes
are disadvantageous with respect to their color strength and
preparability.
The object of the present invention was to provide new brilliant blue
anthraquinone dyes having excellent fastness properties, in particular
chlorine fastness, light fastness and wash fastness, and good fixation
yields, which overcome the abovementioned disadvantages of the prior art.
It has been found that the compounds of the formula (1) defined below
surprisingly meet the necessary requirements.
The present invention relates to anthraquinone compounds of the formula
(1),
##STR3##
in which R.sup.1 is hydrogen, C.sub.1 -C.sub.6 -alkylcarbonyl, C.sub.6
-arylcarbonyl, C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl or
phenyl where C.sub.1 -C.sub.6 -alkyl, C.sub.6 -arylcarbonyl C.sub.3
-C.sub.6 -cycloalkyl and phenyl can be substituted by one or more radicals
selected from the group consisting of hydroxyl, sulfo, carboxyl, C.sub.1
-C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen, cyano, amino and
nitro,
R.sup.2 is sulfo or carboxyl,
m is 0 to 2,
R.sup.3 is sulfo, carboxyl or halogen, such as chlorine or bromine,
n is 0 or 1,
R.sup.4 is sulfo, carboxyl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4
-alkoxy,
p is 0 to 2,
W is a C.sub.1 -C.sub.6 -alkylene group,
Y is vinyl or --CH.sub.2 CH.sub.2 -L in which L is a group which can be
eliminated under alkaline conditions,
M is hydrogen or an alkali metal or a stoichiometric equivalent of an
alkaline earth metal,
q is 0 or 1, and
is halogen, hydroxyl, C.sub.1 -C.sub.4 -alkyloxy, C.sub.6 -aryloxy,
cyanamino, amino, carboxy-(C.sub.1 -C.sub.4)-alkylamino, C.sub.1 -C.sub.4
-alkylamino, di-(C.sub.1 -C.sub.4 -alkyl) amino or C.sub.6 -arylamino
where the alkyl and aryl radicals of the alkylamino and arylamino groups
mentioned are unsubstituted or contain 1 to 5 substituents selected from
the group consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl,
sulfo, sulfato, C.sub.1 -C.sub.4 -alkylsulfonyl, C.sub.6 -arylsulfonyl,
halogen, cyano and nitro, or is the radical of a heterocyclic or aliphatic
amine which may contain 1 to 2 further hetero atoms selected from the
group consisting of N, O and S and can be substituted by a carboxyl
radical or an aminocarbonyl radical, or is the group --NR.sup.9 R.sup.10
R.sup.11 in which R.sup.9, R.sup.10 and R.sup.11, independently of one
another, are hydrogen or C.sub.1 -C.sub.4 -alkyl.
For the purposes of the present invention, preference is given to compounds
of the formula (1) in which
R.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.5 -C.sub.6 -cycloalkyl,
acetyl, benzoyl, phenyl or methylphenylcarbonyl or C.sub.1 -C.sub.4 alkyl,
C.sub.5 -C.sub.6 -cycloalkyl or phenyl each of which is substituted by 1
to 3 radicals selected from the group consisting of hydroxyl, sulfo,
carboxyl, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine,
cyano or nitro.
Particular preference is given to those compounds of the formula (1) in
which
R.sup.1 is hydrogen.
Furthermore, preference is given to compounds of the formula (1) in which
R.sup.3 is a sulfo group which is in the ortho position relative to the
NH-R.sup.1 group.
Furthermore, preference is given to compounds of the formula (1) in which
R.sup.4 is sulfo, carboxyl, methyl, ethyl, methoxy or ethoxy.
Furthermore, preference is given to compounds of the formula (1) in which
W is C.sub.2 -C.sub.3 -alkylene, preferably 1,2-ethylene or 1,3-propylene.
Furthermore, preference is given to compounds of the formula (1) in which
L is chlorine, bromine, --OSO.sub.3 M, --SSO.sub.3 M, --OPO.sub.3 M.sub.2,
preferably --OSO.sub.3 M or chlorine, where M is hydrogen or an alkali
metal.
Furthermore, preference is given to compounds of the formula (1) in which
m is 0,
n is 1,
p is 0 or 1, and
q is 0.
Furthermore, preference is given to compounds of the formula (1) in which
X is fluorine, chlorine, cyanamino, amino, carboxymethylamino,
.beta.-carboxyethylamino, .beta.-sulfoethylamino,
N-methyl-.beta.-sulfoethylamino, .beta.-sulfatoethylamino,
.beta.-hydroxyethylamino, bis(.beta.-hydroxyethyl)amino, pyrrolidino,
piperidino, piperazino, morpholino, pyridin-1-yl, 3-carboxypyridin-1-yl,
3-aminocarbonylpyridin-1-yl or trimethylammonium.
Furthermore, preference is given to compounds of the formula (1) in which
the substituted-O-triazinyl radical is in the para position relative to
the NH group of the phenyl ring.
Particularly preferred dyes are compounds of the formulae (1a), (1b), (1c),
(1d) and (1e)
##STR4##
in which x is 2 or 3,
X.sup.1 is chlorine or fluorine,
R.sup.5 is methyl, ethyl or phenyl,
A is amino, carboxymethylamino, .beta.-carboxyethylamino,
.beta.-sulfoethylamino, N-methyl-.beta.-sulfoethylamino,
.beta.-sulfatoethylamino, .beta.-hydroxyethylamino,
bis(.beta.-hydroxyethyl)eunino, morpholino, piperidino, pyrrolidino or
trimethylammonium,
R.sup.8 is hydrogen, euninocarbonyl or carboxyl,
Y.sup.1 is .beta.-sulfatoethyl, .beta.-chloroethyl or vinyl and R.sup.1 =0
or 1.
Particular preference is given to dyes of the formula (1f)
##STR5##
in which x and Y.sup.1 have one of the abovementioned meanings. The
preferred dyes of the formulae (1a), (1c), (1d), (1e) and (1f) have the
advantage that they do not contain any organically bound halogen if
Y.sup.1 is .beta.-sulfatoethyl or vinyl, i.e. they are ecologically
particularly advantageous.
Furthermore, the present invention provides a process for preparing the
anthraquinone dyes according to the invention (1), which process comprises
reacting a compound of the formula (2)
##STR6##
in which A is fluorine, chlorine, bromine, iodine, sulfo or nitro, in
particular bromine, and the radicals R.sup.1, R.sup.2 and R.sup.3 have one
of the abovementioned meanings with a compound of the formula (3)
##STR7##
in which R.sup.4 and p have one of the abovementioned meanings, in the
presence of a copper(I) or a copper(II) compound or a mixture thereof, to
give a compound of the formula (4)
##STR8##
reacting the compound of the formula (4) either with a compound of the
formula (5)
##STR9##
in which X, W, Y, M and q have one of the abovementioned meanings and
X.sup.2 is halogen, to give the compound of the formula (1), or reacting
the compound of the formula (4) first with a compound of the formula (6)
##STR10##
in which X and X.sup.2 have the abovementioned meanings, to give a
compound of the formula (7)
##STR11##
and reacting the compound of the formula (7) with an amine of the formula
(8)
##STR12##
in which W, Y, M and q have one of the abovementioned meanings, to give
the compound of the formula (1).
The preferred process variant for preparing the anthraquinone compounds of
the formula (1) is the route described above via the compounds of the
formulae (6), (7) and (8).
It is known from the literature that Ullmann condensations of bromamine
acid with aromatic amines are best carried out in the presence of
copper(I) compounds (J.Chem. Soc. Perkin II, 1974, 676 and Coll. Czech.
Chem. Commun. 46 (1981), 92). Preferably, a catalytic amount, for example
0.5 to 5% by weight, preferably 0.8 to 2% by weight, relative to the
compound of the formula (2), of a copper(I) compound, preferably of a
copper(I) halide or a copper(I) pseudohalide, such as CuCl, CuBr, CuI or
CuCN, is used and the condensation is carried out at temperatures of
30.degree. to 90.degree. C., preferably 50.degree. to 70.degree. C., and
pH values of 5 to 10, preferably 6 to 9.
It has now been found that the condensation of the compounds of the
formulae (2) and (3) can surprisingly also be carried out in the presence
of copper (II) compounds, such as copper (II) sulfate, copper (II)
nitrate, copper (II) chloride, copper (II) bromide, copper (II) carbonate
or copper (II) hydroxide.
Accordingly, the present invention also provides a process for preparing a
compound of the formula (4) by condensing a compound of the formula (2)
with a compound of the formula (3) in the presence of a copper(II)
compound. Also in the case where a copper(II) compound is used, it
preferred to choose the amounts, temperatures and pH values mentioned for
the case of using a copper(I) compound.
Not only when copper(I) compounds but also when copper(II) compounds are
used, the condensation is carried out in an aqueous or aqueous organic
medium in suspension or solution. If the reaction is carried out in an
aqueous organic medium, the organic medium is, for example, acetone,
dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.
Advantageously the hydrohalic acid released during condensation is
continuously neutralized by adding aqueous alkali metal hydroxides, alkali
metal carbonates, alkali metal phosphates, alkali metal silicates or
alkali metal bicarbonates. The relative molar amounts of the compounds of
the formulae (2) and (3) are advantageously 1:1 to 1:1.4.
The reaction of the compound of the formula (4) with the compound of the
formula (5) is advantageously carried out at temperatures of 50.degree. to
100.degree. C. and pH values of 3 to 7, if X.sup.2 is chlorine or bromine,
and advantageously at temperatures of -5.degree. to 50.degree. C.,
preferably 0.degree. to 25.degree. C., and pH values of 4 to 10, if
X.sup.2 is fluorine. The relative molar amounts of the compounds of the
formulae (4) and (5) are advantageously 1:1 to 1:1.5.
The reaction of the compound of the formula (4) with the compound of the
formula (6) is advantageously carried out at temperatures of 0.degree. to
50.degree. C., preferably 20.degree. to 40.degree. C., and pH values of 4
to 10, preferably 7 to 9, if X.sup.2 is chlorine or bromine, and
advantageously at temperatures of -5.degree. to 25.degree. C., preferably
-2.degree. to +5.degree. C., and pH values of 3 to 5, if X.sup.2 is
fluorine. The relative molar amounts of the compounds of the formulae (4)
and (6) are advantageously 1:1 to 1:1.5.
The reaction of the compound of the formula (7) with the amine of the
formula (8) can be carried out under surprisingly mild conditions, at
temperatures of 30.degree. to 90.degree. C., preferably 40.degree. to
70.degree. C., and pH values of 4 to 7, preferably 5 to 6. The relative
molar amounts of the compounds of the formulae (7) and (8) are
advantageously 1:1 to 1:1.5.
The anthraquinone dyes of the formula (I) according to the invention are
precipitated, for example, by pouring them onto ice/water with stirring.
Neutralization with alkali metal hydroxide, alkali metal phosphate, alkali
metal silicate, alkali metal carbonate or alkali metal bicarbonate gives
the aqueous solutions of the alkali metal salts of the compounds of the
formula (1). The dyes can be isolated from this solution, for example, by
salting out or by spray drying. It is particularly advantageous to use the
standardized aqueous formulations, to which, if desired, buffer substances
are added and which, if desired, can be concentrated, directly for the
corresponding technical applications.
Anthraquinone dyes of the formula (1) in which X is the radical of one the
amines defined above (X=X.sup.10) can also be prepared by first preparing
the corresponding anthraquinone dye of the formula (1) in which X is
chlorine or fluorine (X=X.sup.2) by one of the methods mentioned and then
reacting this dye with the corresponding amine at temperatures of
40.degree. to 100.degree. C. and pH values of 3 to 8 in relative molar
amounts of, advantageously, 1:1 to 1:2.
Examples of such amines mentioned include the following: ammonia,
methylamine, ethylamine, ethanolamine, diethanolamine,
.beta.-sulfoethylamine, N-methyl-.beta.-sulfoethylamine,
.beta.-carboxyethylamine, carboxymethylamine, 3-carboxypyridine,
3-aminocarbonylpyridine, pyridine, morpholine, pyrrolidine, piperidine,
piperazine, N'-hydroxyethylpiperazine, N'-sulfatoethylpiperazine, aniline,
3-sulfoaniline, 4-sulfoaniline, 4-carboxyaniline, 4-methylaniline,
4-methoxyaniline, 4-methoxy-3-sulfoaniline and 4-methyl-3-sulfoaniline.
Accordingly, the invention also provides a process for preparing an
anthraquinone compound of the formula (1A)
##STR13##
in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, W, Y, M, m, n, p and q have
one of the meanings defined in claim 1 and X.sup.10 is amino, cyanamino,
carboxy-(C.sub.1 -C.sub.4)-alkylamino, C.sub.1 -C.sub.4 -alkylamino,
di-(C.sub.1 -C.sub.4 -alkyl)amino, C.sub.6 -arylamino where the alkyl and
aryl radicals of the alkylamino and arylamino groups mentioned are
unsubstituted or contain 1 to 5 substituents selected from the group
consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl, sulfo,
sulfato, C.sub.1 -C.sub.4 -alkylsulfonyl, C.sub.6 -arylsulfonyl, halogen,
cyano and nitro, or is the radical of a heterocyclic or aliphatic amine,
which may contain 1 to 2 further hetero atoms selected from the group
consisting of N, O and S and can be substituted by a carboxyl radical or
an aminocarbonyl radical, or is the group -NR.sup.9 R.sup.10 R.sup.11 in
which R.sup.9, R.sup.10 and R.sup.11, independently of one another, are
hydrogen or C.sub.1 -C.sub.4 -alkyl,
which process comprises reacting an anthraquinone compound of the formula
(1B)
##STR14##
in which X.sup.20 is chlorine or fluorine, with ammonia, H.sub.2 NCN, a
carboxy-(C.sub.1 -C.sub.4)alkylamine, C.sub.1 -C.sub.4 -alkylamine,
di-(C.sub.1 -C.sub.4 -alkyl)amine, C.sub.6 -arylamine where the alkyl and
aryl radicals of the alkylamino and arylamino groups mentioned are
unsubstituted or contain 1 to 5 substituents selected from the group
consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl, sulfo,
sulfato, C.sub.1 -C.sub.4 -alkylsulfonyl, C.sub.6 -arylsulfonyl, halogen,
cyano and nitro, or with a heterocyclic or aliphatic amine, which may
contain 1 to 2 further hetero atoms selected from the group consisting of
N, O and S and can be substituted by a carboxyl radical or an
aminocarbonyl radical, or with a mono-, di- or tri-(C.sub.1 -C.sub.4
-alkyl)ammonium salt.
Examples of compounds of the formula (2) include the following:
1-amino-4-bromo-, 1-amino-4-bromo-2-sulfo-, 1-amino-2,4-dibromo-,
1-methylamino-2-carboxy-4-bromo-, 1-ethylamino-2-carboxy-4-bromo-,
1-isopropylamino-2-carboxy-4-bromo-, 1-amino-4-bromo-2,6-disulfo-,
1-amino-4-bromo-2,7-disulfo-, 1-amino-4-bromo-2,5,8-trisulfo-,
1-propylamino-4-bromo-2-sulfo-, 1-amino-4-bromo-2-carboxy-,
1-amino-4-bromo-2-sulfo-6-carboxy-, 1-amino-4-bromo-2-sulfo-7-carboxy-,
1-methylamino-4-bromo-, 1-methylamino-4-bromo-2-sulfo-,
1-ethylamino-4-bromo-2-sulfo-,
1-(.beta.-hydroxyethyl)amino-4-bromo-2-sulfo-,
1-phenylamino-4-bromo-2-sulfo-, 1-amino-2-bromo-4-nitro-,
1-cyclohexylamino-4-bromo-, 1-benzoylamino-4-bromo-,
1-acetylamino-4-bromo-, 1-cyclohexylamino-4-bromo-5-sulfo-,
1-cyclohexylamino-4-bromo-6-sulfo-, 1-cyclohexylamino-4-bromo-7-sulfo- or
1-cyclohexylamino-4-bromo-8-sulfoanthraquinone.
A particularly preferred anthraquinone component is
1-amino-4-bromo-2-sulfoanthraquinone. The preparation of the anthraquinone
compounds mentioned is known to one skilled in the art and described, for
example, in Houben-Weyl, Vol. 7/3c, 4th. Edition, p. 46ff.
Examples of compounds of the formula (3) are 4-aminophenol,
4-amino-2-sulfophenol, 4-amino-3-sulfophenol, 3-aminophenol,
3-amino-4-sulfophenol, 3-amino-5-sulfophenol, 2-carboxy-4-aminophenol and
3-carboxy-4-aminophenol. The preparation of such aminophenols is known to
one skilled in the art and described, for example, in Houben-Weyl, Vol.
XI/1.
Compounds of the formula ( 5 ) can be prepared, for example, by reacting
compounds of the formula (6) with compounds of the formula (8)
(EP-A1-0,629,667).
Examples of compounds of the formula (6) are
2,4,6-trichloro-1,3,5-triazine, 2,4,6-trifluoro-1,3,5-triazine,
2-cyanamino-4,6-dichloro-1,3,5-triazine,
2-methoxy-4,6-dichloro-1,3,5-triazine,
2-ethoxy-4,6-dichloro-1,3,5-triazine,
2-phenoxy-4,6-dichloro-1,3,5-triazine and
2-amino-4,6-dichloro-1,3,5-triazine. The preparation of such triazines is
known to one skilled in the art and described, for example, in
DE-A-2,756,438 and DE-A-3,930,704.
Examples of compounds of the formula (8) are 3-(N-phenyl)aminopropyl
2'-sulfatoethyl sulfone, 3-N-[3"-sulfophenyl]aminopropyl 2'-sulfatoethyl
sulfone, 3-N-[4"-sulfophenyl]aminopropyl 2'-sulfatoethyl sulfone,
3-N-[2"-sulfophenyl)aminopropyl 2'-sulfatoethyl sulfone,
2-(N-phenyl)aminoethyl 2'-sulfatoethyl sulfone,
2-N-[2"-sulfophenyl]aminoethyl 2'-sulfatoethyl sulfone,
2-N-[3"-sulfophenyl]aminoethyl 2'-sulfatoethyl sulfone and
2-N-[4"-sulfophenyl]aminoethyl 2'-sulfatoethyl sulfone. The preparation of
such compounds is described, for example, in EP-A1-0,629,667 and
EP-A1-0,568,876.
The compounds of the formula (1) exhibit fiber-reactive properties and
possess very good dye properties. They can be used for dyeing and printing
hydroxyl-, mercapto-, amino- and/or carboxamido-containing materials, in
particular fiber materials. They give brilliant blue shades having
excellent fastness properties, such as light fastness, wash fastness and
chlorinated water fastness without requiring metal complexations.
Accordingly, the dyes according to the invention are ecologically
advantageous.
Accordingly, the present invention also relates to the use of the compounds
of the formula (1) for dyeing and printing the materials mentioned. This
is done by applying the compound of the formula (1) to the material or
incorporating it in the material and fixing it on or in the material by
means of heat or by using an alkaline agent.
Examples of suitable materials are native or regenerated cellulose
materials, such as cotton, linen, staple viscose, filament viscose,
chemically modified cellulose fibers, for example cellulose fibers
modified by amino compounds, proteinaceous fibers, such as wool or silk,
and synthetic polyamides, such as nylon or perlon, all of which are well
known to one skilled in the art.
Examples of suitable application methods are the exhaust method in
winch-dyeing machines and jet-dyeing machines or continuous dyeing
methods. The dyes according to the invention are particularly suitable for
dyeing and printing cellulose materials using a short-liquor application
method, for example at a liquor ratio of 0,4:1 to 5:1, and for textile
printing or pad-dyeing methods, such as, for example, continuous methods.
The preferred dyes (1a), (1c), (1d), (1e) and especially (1f) are
particularly suitable for textile printing methods. Another characteristic
feature of the preferred dyes (1a), (1c), (1d), (1e) and especially (1f)
is that they can advantageously be applied in the discharge printing
method.
In this description, the dyes of the present invention have been written in
the form of their free acids. However, they can also be used as salts of
these acids. Preferably, they are used in the form of their salts, and
particularly preferably in the form of their alkali metal salts and
alkaline earth metal salts, such as, for example, their sodium salts,
potassium salts or lithium salts.
In the examples, percentages and parts are by weight. The absorption maxima
given (lambda max) in the visible region were determined using their
alkali metal salts in aqueous solution.
Example A
38.2 parts of 1-amino-4-bromo-2-sulfoanthraquinone (bromamine acid) are
condensed in an aqueous suspension with 12.7 parts of 4-aminophenol with
the addition of 1 part of copper(II) sulfate at a pH of 8.5 and a
temperature of 70.degree. C. over a period of 1 to 2 hours. This results
in a dark blue solution. After cooling to 20.degree.-25.degree. C., the
reaction mixture is acidified until reaching a pH of about 1, stirred at
60.degree. C. for about 1 h, salted out with sodium chloride, and the dye
chromophore 4-(4'-hydroxyphenyl)amino-1-amino-2-sulfoanthraquinone is
isolated by suction filtration.
The anthraquinone compound thus obtained has the formula
##STR15##
Example 1
41 parts of the anthraquinone compound from Example A are dissolved in 200
parts of water at a pH of 8.5 and a temperature of 35.degree. C., followed
by addition of 20 parts of 2-cyanamino-4,6-dichloro-1,3,5-triazine and
condensation at a pH of 8 to 9 and a temperature of 35.degree. C. The
mixture is stirred for some time until reaction is complete, and 36 parts
of 3-(N-phenyl)aminopropyl 2'-sulfatoethyl sulfone are then added. The
reaction is carried out at a temperature of 50.degree. C. and a pH of 8.5
over a period of about 3 h. The product is then salted out with potassium
chloride or, preferably, isolated by evaporation in vacuo to give 85 parts
of the dye of the formula
##STR16##
in an HPLC purity of 90%.
The dye dyes and prints cellulose fibers in brilliant blue shades which
exhibit high color strengths in combination with good levelness and very
good fastness properties, in particular light fastness properties.
Example 2
41 parts of the anthraquinone compound from Example A are dissolved in 200
parts of water at a pH of 8.5 and a temperature of 40.degree. C., followed
by addition of 20 parts of 2-cyanamino-4,6-dichloro-1,3,5-triazine and
condensation at a pH of 8 to 9 and a temperature of 40.degree. C. The
mixture is stirred for some time until reaction is complete, and 33 parts
of 2-(N-phenyl)aminoethyl 2'-sulfatoethyl sulfone are then added. The
reaction is carried out at a temperature of 50.degree. C. and a pH of 8.5
over a period of about 3 h. The product is then salted out with potassium
chloride or, preferably, isolated by evaporation in vacuo to give 82 parts
of the dye of the formula
##STR17##
in an HPLC purity of 84%.
The dye dyes and prints cellulose fibers in brilliant blue shades which
exhibit high color strengths in combination with good levelness and very
good fastness properties, in particular light fastness properties.
Example 3
41 parts of the anthraquinone compound from Example A are dissolved in 200
parts of water at a pH of 8.5 and a temperature of 40.degree. C., followed
by addition of 20 parts of 2,4,6-trichloro-1,3,5-triazine and condensation
at a pH of 7 to 8 and a temperature of 0.degree. to 5.degree. C. The
mixture is stirred for some time until reaction is complete, and 33 parts
of N-phenyl-2-[(2'-sulfatoethyl)sulfonyl]-ethylamine are then added. The
reaction is carried out at a temperature of 50.degree. C. and a pH of 8.5
over a period of about 3 h. The product is then salted out with potassium
chloride or, preferably, isolated by evaporation in vacuo to give 82 parts
of the dye of the formula
##STR18##
in an HPLC purity of 87%.
The dye dyes and prints cellulose fibers in brilliant blue shades which
exhibit high color strengths in combination with good levelness and very
good fastness properties, in particular light fastness properties.
Example 4
87 parts of the compound from Example 3 are dissolved in 300 parts of water
at a pH of 6.5 and a temperature of 30.degree. C., followed by addition of
8.5 parts of morpholine and condensation at a pH of 7 to 8 and a
temperature of 60.degree. C. The mixture is stirred for some time until
reaction is complete. The product is then salted out with potassium
chloride or, preferably, isolated by evaporation in vacuo to give 85 parts
of the dye of the formula
##STR19##
in an HPLC purity of 73%.
The dye dyes and prints cellulose fibers in brilliant blue shades which
exhibit high color strengths in combination with good levelness and very
good fastness properties, in particular light fastness properties.
Example 5
41 parts of the anthraquinone compound from Example A are dissolved in 500
parts of water at a pH of 8 and a temperature of 30.degree. C. and cooled
to 0.degree. to 5.degree. C., followed by addition of 45 parts of the
compound
2-[N-phenyl-(2'-sulfatoethylsulfonyl)ethylamino]-4,6-difluoro-1,3,5-triazi
ne disclosed in EP-A-0,568,876 and condensation at a pH of 7 to 8 and a
temperature of 10.degree. to 20.degree. C. The mixture is stirred for some
time until reaction is complete. The product is then salted out with
potassium chloride or, preferably, isolated by evaporation in vacuo to
give 80 parts of the dye of the formula
##STR20##
in an HPLC purity of 88%.
The dye dyes and prints cellulose fibers in brilliant blue shades which
exhibit high color strengths in combination with good levelness and very
good fastness properties, in particular light fastness properties.
Example 6
80 parts of the compound from Example 5 are dissolved in 300 parts of water
at a pH of 6.5 and a temperature of 30.degree. C., followed by addition of
12 parts of nicotinic acid and condensation at a pH of 3 to 4 and a
temperature of 70.degree. to 80.degree. C. The mixture is stirred for some
time until reaction is complete. The product is then salted out with
potassium chloride or, preferably, isolated by evaporation in vacuo to
give 90 parts of the dye of the formula
##STR21##
in an HPLC purity of 73%.
The dye dyes and prints cellulose fibers in brilliant blue shades which
exhibit high color strengths in combination with good levelness and very
good fastness properties, in particular light fastness properties.
Further dyes of the following formula according to the invention are
obtained by repeating the procedure of Example 1 and using for the
synthesis the corresponding precursors shown in the table.
__________________________________________________________________________
##STR22##
Ex. Shade
No.
B(1 = amino linkage)
X.sup.0 N(Ar)W.sup.1 SO.sub.2 Y
on cotton
__________________________________________________________________________
7 1,4-phenylene
chlorine N-phenyl-[3'-(.beta.-
blue
sulfatoethyl)-
(602)
sulfonyl-
propyl]amino
8 " cyanamino N-(3"- blue
sulfophenyl)-[3'-
(604)
(.beta.-sulfatoethyl)-
sulfonylpropyl]-
amino
9 " cyanamino N-(3"- blue
sulfophenyl)-[2'-
(605)
(.beta.-sulfatoethyl)-
sulfonylethyl]-
amino
10 1,3-phenylene
fluorine N-phenyl-[3'-(.beta.-
blue
sulfatoethyl)
(605)
sulfonylpropyl]-
amino
11 3-sulfo- amino N-phenyl-[3'-(.beta.-
blue
1,4-phenylene sulfatoethyl)
(606)
sulfonylpropyl]-
amino
12 3-sulfo- piperidino
N-phenyl-[3'-(.beta.-
blue
1,4-phenylene sulfatoethyl)
(603)
sulfonylpropyl]-
amino
13 4-sulfo- pyrrolidino
N-phenyl-[3'-(.beta.-
blue
1,3-phenylene sulfatoethyl)
(603)
sulfonylpropyl]-
amino
14 1,4-phenylene
(3-amino- N-phenyl-[3'-(.beta.-
blue
carbonyl)-pyridinyl
sulfatoethyl)-
(603)
sulfonyl-
propyl]amino
15 " methoxy N-phenyl-[3'-(.beta.-
blue
sulfatoethyl)-
(603)
sulfonyl-
propyl]amino
16 " phenoxy N-phenyl-[3'-(.beta.-
blue
sulfatoethyl)-
(603)
sulfonyl-
propyl]amino
__________________________________________________________________________
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